JPH05346646A - Treatment of silver halide monochromatic photosensitive material - Google Patents

Abstract

PURPOSE:To provide a treating method for a super-hard silver halide monochromatic photosensitive material without causing production of sludge or bad treatment in the process with using an automatic developing machine. CONSTITUTION:A silver halide monochromatic photosensitive material having at least one silver halide emulsion layer on a supporting body is exposed to light for patterning, developed with a developer, and treated with a treating liquid having fixing ability. In this process, the structural layer of the silver halide monochromatic photosensitive material contains a hydrazine deriv., and the developer and/or the treating liquid having fixing ability contains a nonion surfactant.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide black and white photographic light-sensitive material, and more particularly to a processing method for preventing sludge in processing a light-sensitive material for printing plate making.

[0002]

BACKGROUND OF THE INVENTION The photomechanical process involves the conversion of continuous tone originals into halftone images. In this process, a technique based on infectious development has been used as a photographic technique capable of reproducing an image in ultra-high contrast.

The lithographic silver halide photographic light-sensitive material used for infectious development has, for example, an average particle size of about 0.2 μm, a narrow particle distribution and a well-formed particle shape, and a high silver chloride content (at least 50). Mol% or more) consisting of silver chlorobromide emulsion,
If necessary, water-soluble iridium or rhodium is added during particle formation. By processing such a lith-type silver halide photographic light-sensitive material with an alkaline hydroquinone developer having a low sulfite ion concentration, a so-called lith-type developer, an image having high contrast, high sharpness and high resolution can be obtained.

However, since these lith-type developers are susceptible to air oxidation and have extremely poor preservability, it is difficult to keep the development quality constant during continuous use.

There is known a method of rapidly obtaining a high-contrast image without using the lith developer. For example, as disclosed in JP-A-56-106244, a method of incorporating a hydrazine derivative into a silver halide photographic light-sensitive material. According to these methods, it is possible to obtain a high-contrast image having good preservability and rapid processing.

However, in the case of a super-high-contrast silver halide photographic light-sensitive material using such a hydrazine derivative, it often becomes insoluble in the processing liquid, and when processed by an automatic processor, sludge is deposited on the rollers of the automatic processor. As a result, there is a problem in that it adheres or causes a processing failure.

[0007]

SUMMARY OF THE INVENTION In order to solve the above problems, an object of the present invention is to provide a processing method for super-high-contrast silver halide black-and-white photographic light-sensitive material which does not cause sludge and processing defects in processing by an automatic processor. To provide.

[0008]

The above object of the present invention has a fixing ability after imagewise exposing a silver halide black-and-white photographic light-sensitive material having at least one silver halide emulsion layer on a support and processing it with a developer. In the processing method of processing with a processing solution, a nonionic surfactant is added to the processing solution containing a hydrazine derivative in the constituent layer of the silver halide black and white photographic light-sensitive material and having the developing solution and / or the fixing ability. It is achieved by a method for processing a silver halide black-and-white photographic light-sensitive material characterized by containing.

The hydrazine derivative used in the present invention is preferably a compound represented by the following general formula [H].

[0010]

[Chemical 1]

In the present invention, among these, the following general formula [H-a], [H-b], [H-c] or [H-] is further used.
The compound represented by d] is preferable.

[0012]

[Chemical 2]

In the above general formula [Ha], R ₃ and R ₄ are each a hydrogen atom, a substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, butyl group, dodecyl group, 2-hydroxypropyl group, 2 -Cyanoethyl group, 2-chloroethyl group), substituted or unsubstituted phenyl group, naphthyl group, cyclohexyl group, pyridyl group, pyrrolidyl group (eg phenyl group, p-methylphenyl group, naphthyl group, α
-Hydroxynaphthyl group, cyclohexyl group, p-methylcyclohexyl group, pyridyl group, 4-propyl-2-pyridyl group, pyrrolidyl group, 4-methyl-2-pyrrolidyl group) and the like, R ₅ is a hydrogen atom, a substituent or Represents an unsubstituted benzyl group, an alkoxy group or an alkyl group (for example, a benzyl group, a p-methylbenzyl group, a methoxy group, an ethoxy group, an ethyl group, a butyl group), and R ₆ and R ₇ are each 2
Represents a valent aromatic group (for example, a phenylene group or a naphthylene group), Y represents a sulfur atom or an oxygen atom, and L
The divalent linking group (e.g., _{-SO 2 CH 2 CH 2 NH -} , - SO 2 NH-,
_{-OCH 2 SO 2 NH -, -} O -, - CH = N-) represents, R ₈ is -N
R′R ″ or —OR ₉ is represented, and R ′, R ″ and R ₉ are each a hydrogen atom, a substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, dodecyl group), phenyl group (eg, phenyl group, p-methylphenyl group, p-methoxyphenyl group), naphthyl group (eg α-naphthyl group, β-naphthyl group) or heterocyclic group (eg unsaturated heterocyclic group such as pyridine, thiophene, furan or tetrahydrofuran, sulfolane R ′ and R ″ may form a ring (eg piperidine, piperazine, morpholine, etc.) together with the nitrogen atom.

M and n each represent 0 or 1.
Y When R ₈ represents -OR ₉ preferably represents a sulfur atom.

[0015]

[Chemical 3]

In the formula, R ₁₀ , R ₁₁ and R ₁₂ are each a hydrogen atom, an alkyl group (for example, a methyl group, an ethyl group, a butyl group, a 3-aryloxypropyl group), a substituted or unsubstituted phenyl group and a naphthyl group. , Cyclohexyl group, pyridyl group, pyrrolidyl group, substituted or unsubstituted alkoxy group (eg methoxy group, ethoxy group, butoxy group)
Alternatively, it represents a substituted or unsubstituted aryloxy group (eg, phenoxy group, 4-methylphenoxy group).

In the present invention, R ₁₂ is preferably a hydrogen atom or an alkyl group.

R ₁₃ represents a divalent aromatic group (eg, phenylene group, naphthylene group), and Z represents a sulfur atom or an oxygen atom.

R ₁₄ is a substituted or unsubstituted alkyl group,
It represents an alkoxy group or an amino group, and examples of the substituent include an alkoxy group, a cyano group and an aryl group.

The hydrazine derivative can be easily synthesized by a known method. For example, JP-A-2-214850.
No. 2-47646, No. 2-12237 and the like.

Representative compounds represented by the above general formulas [Ha-] and [H-b] are shown below.

[0022]

[Chemical 4]

[0023]

[Chemical 5]

[0024]

[Chemical 6]

[0025]

[Chemical 7]

[0026]

[Chemical 8]

[0027]

[Chemical 9]

[0028]

[Chemical 10]

[0029]

[Chemical 11]

In the formula, A represents an aryl group or a heterocyclic group containing at least one sulfur atom or oxygen atom, and n represents an integer of 1 or 2. When n = 1, R ₁₅ and R ₁₆ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, Or a heterocyclic oxy group, R ₁₅ and R
₁₆ may form a ring with a nitrogen atom. When n = 2,
R ₁₅ and R ₁₆ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a saturated or unsaturated heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or hetero. Represents a ring oxy group. However, when n = 2, R ₁₅ and R
_At least one of ₁₆ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or a heterocyclic oxy group. R ₁₇ represents an alkynyl group or a saturated heterocyclic group.

The compound represented by the general formula [Hc] or [Hd] includes a compound in which at least one H of -NHNH- in the formula is substituted with a substituent.

More specifically, A is an aryl group (eg, phenyl, naphthyl, etc.) or a heterocyclic group containing at least one sulfur atom or oxygen atom (eg, thiophene, furan, benzothiophene, pyran, etc.). Represents.

R ₁₅ and R ₁₆ are each a hydrogen atom, an alkyl group (eg, methyl, ethyl, methoxyethyl, cyanoethyl, hydroxyethyl, benzyl, trifluoroethyl, etc.), an alkenyl group (eg, allyl, butenyl, pentenyl, pentadienyl). Etc.), an alkynyl group (eg, propargyl, butynyl, pentynyl, etc.),
Aryl groups (eg, phenyl, naphthyl, cyanophenyl, methoxyphenyl, etc.), heterocyclic groups (eg, unsaturated heterocyclic groups such as pyridine, thiophene, furan and saturated heterocyclic groups such as tetrahydrofuran, sulfolane),
Hydroxy group, alkoxy group (eg, methoxy, ethoxy, benzyloxy, cyanomethoxy, etc.), alkenyloxy group (eg, allyloxy, butenyloxy, etc.), alkynyloxy group (eg, propargyloxy, butynyloxy, etc.), aryloxy group (eg, ,
Phenoxy, naphthyloxy, etc.) or a heterocyclic oxy group (eg, pyridyloxy, pyrimidyloxy, etc.), and when n = 1, R ₁₅ and R ₁₆ together with the nitrogen atom form a ring (eg, piperidine, piperazine, morpholine, etc.) May be formed.

However, when n = 2, at least one of R ₁₅ and R ₁₆ is an alkenyl group, alkynyl group, saturated heterocyclic group, hydroxy group, alkoxy group, alkenyloxy group, alkynyloxy group, aryloxy group or hetero. It represents a ring oxy group.

Specific examples of the alkynyl group and saturated heterocyclic group represented by R ₁₇ include those mentioned above.

Various substituents can be introduced into the aryl group represented by A or the heterocyclic group having at least one sulfur atom or oxygen atom. Examples of the substituent that can be introduced include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an alkylthio group, an arylthio group, a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, and a sulfamoyl group, Acyl group, amino group, alkylamino group, arylamino group, acylamino group, sulfonamide group, arylaminothiocarbonylamino group,
Examples thereof include a hydroxy group, a carboxy group, a sulfo group, a nitro group and a cyano group. Among these substituents, the sulfonamide group is preferred.

In each of the general formulas, A preferably contains at least one diffusion resistant group or silver halide adsorption promoting group. As the anti-diffusion group, a ballast group commonly used in a non-moving photographic additive such as a coupler is preferable. The ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, and is selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. You can

Examples of the silver halide adsorption promoting group include groups described in US Pat. No. 4,385,108 such as thiourea group, thiourethane group, heterocyclic thioamide group, mercaptoheterocyclic group and triazole group.

--NH in the general formulas [Hc] and [Hd]
H of NH-, that is, the hydrogen atom of hydrazine, is a sulfonyl group (for example, methanesulfonyl, toluenesulfonyl, etc.),
Acyl groups (eg acetyl, trifluoroacetyl,
Ethoxycarbonyl, etc.), an oxalyl group (eg, ethoxalyl, pyruvoyl, etc.) and the like, and the compounds represented by the general formulas [Hc] and [Hd] are such compounds. Also includes.

More preferable compounds in the present invention are the compounds of the general formula [Hc] when n = 2, and the compounds of the general formula [Hd].

In the compound of the general formula [H-c] with n = 2, R ₁₅ and R ₁₆ are hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, saturated or unsaturated heterocyclic group, hydroxy group, Or an alkoxy group, and R ₃₁
Further, a compound in which at least one of R ₃₂ and R ₃₂ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group, or an alkoxy group is more preferable.

Typical compounds represented by the above general formulas [Hc] and [Hd] are shown below.
However, as a matter of course, the specific compounds of the general formulas [Hc] and [Hd] that can be used in the present invention are not limited to these compounds.

Specific compound examples

[0044]

[Chemical formula 12]

[0045]

[Chemical 13]

[0046]

[Chemical 14]

[0047]

[Chemical 15]

Specific compounds other than the above are disclosed in
2-841 No. 542 (4) to 546 (8) compound examples
There are (1) to (61) and (65) to (75).

The hydrazine derivative in the present invention is disclosed in
It can be synthesized by the method described in pages 2-841, 546 (8) to 550 (12). The addition position of the hydrazine derivative of the present invention is the silver halide emulsion layer and / or the adjacent layer. The addition amount is preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻¹ mol per mol of silver, and more preferably 1 × 10 ⁻⁵ mol to 1 per mol of silver.
× 10 ^-2 mol.

When [Hc] or [Hd] is contained as a hydrazine derivative, it is disclosed in JP-A-4-98239.
At least one of the nucleation-accelerating compounds described in (7) page lower left line 1 to 626 (26) page lower left line 11 is applied to the silver halide emulsion layer and / or the silver halide emulsion layer side on the support. It is preferably included in a certain non-photosensitive layer.

In the light-sensitive material of the present invention, at least one conductive layer is preferably provided on the support. As a typical method for forming the conductive layer, a water-soluble conductive polymer,
There are a method of forming using a hydrophobic polymer and a curing agent and a method of forming using a metal oxide. For these methods, it is preferable to use the methods described in JP-A-3-265842, page (5) to page (15). The conductive layer is preferably provided on the opposite side of the support from the emulsion layer.

Next, the nonionic surfactant used in the present invention will be described.

The nonionic surfactant used in the present invention exhibits surface activity without being ionized in an aqueous solution, and in addition to natural saponin, as a preferred example, the following general formula [1] To the compound represented by [8].

[0054]

[Chemical 16]

In the formulas [1] to [8], R represents a hydrogen atom or a monovalent organic group. Examples of the organic group include a linear or branched alkyl group having 1 to 30 carbon atoms, which may have a substituent {for example, an aryl group (phenyl etc.)}, and an alkylcarbonyl in which the alkyl moiety is the above alkyl group. Examples thereof include a group and a phenyl group which may have a substituent (for example, a hydroxyl group, the above-mentioned alkyl group and the like). a, b, c, m, n, x and y are each 1 to 40
Represents the integer.

Specific examples of the nonionic surfactant used in the present invention are shown below.

NS-1 Saponin NS-2 Polyethylene glycol NS-3 Polyoxyethylene lauryl ether NS-4 Polyoxyethylene stearyl ether NS-5 Polyoxyethylene polyoxypropylene cetyl ether NS-6 Polyoxyethylene nonylphenyl ether NS- 7 Polyoxyethylene octyl phenyl ether NS-8 Polyoxyethylene stearylamine NS-9 Polyoxyethylene oleic acid amide NS-10 Polyoxyethylene glycer monostearate NS-11 Polyoxyethylene propylene glycol monostearate NS-12 Oxyethylene Oxypropylene block polymer NS-13 Octylphenol polyoxyethylene polyoxypropylene adduct NS-14 sorbitan monolaurate NS-15 polyoxyethylene monolaurate The emissions-based compounds, and other U.S. Patent No. 2,567,848 also the 2,739,172 Patent, the 2,588,771
No., No. 2,596,091, No. 2,498,617, No. 2,473,798,
2,616,921, 2,603,653, 2,710,861, 2,6
38,404, 2,520,381, 2,258,892, 2,662,07
No. 3, No. 2,584,751, No. 2,587,340, No. 2,629,704,
2,505,823, 26,061,202, 2,425,845, 2,
673,882, 3,272,628, 3,294,540, 3,516,8
The compounds described in JP-A Nos. 30 and 3,518,085, JP-A-49-9236 and the like can be mentioned.

When the nonionic surfactant of the present invention is contained in a developing solution or a fixing solution, alcohols such as methanol and ethanol, triethylene glycol,
It may be added after being dissolved in a glycol such as diethylene glycol or an appropriate organic solvent such as acetone or cellosolve.

Especially when the nonionic surfactant of the present invention is contained in the developing solution and / or the fixing solution,
The content is 01 mg / l to 100 g / l, preferably 1 mg / l to 10 g / l. The nonionic surfactant of the present invention can be added to a plurality of processing solutions, but it is preferably added to at least the developing solution.

The silver halide emulsion used in the present invention (hereinafter referred to as a silver halide emulsion or simply an emulsion etc.) includes, for example, silver bromide, silver iodobromide, silver iodochloride, chloroodor. Any of silver halide, silver chloride and the like used for ordinary silver halide emulsions can be used, but monodisperse emulsions are preferable, and the grain size is 1 μm or less, especially 0.0
8-0.5 μm is preferred.

In the light-sensitive material of the present invention, the total amount of gelatin on the emulsion layer side is preferably 3.0 g / m ² or less. The emulsion layer side means the side of the layer having a silver halide emulsion with respect to the support, and includes the silver halide emulsion layer and other layers. Examples of the other layer include an emulsion protective layer, an antihalation layer, a UV absorption layer, an intermediate layer, and a conductive layer. The total amount of gelatin contained in the silver halide emulsion layer and others is 3.0 g / m ² or less, preferably 1.8 to 2.9 g / m
^{Is 2} .

Various additives can be used in the light-sensitive material of the present invention depending on the purpose.

More specifically, these additives are described in Research Disclosure Vol. 176, Item 17643 (December 1978).
187 and Vol. 187, Item 18716 (November, 1979), the relevant parts are summarized below.

Additive type RD17643 RD18716 1. Chemical sensitizer Page 23 Page 648 Right column 2. Sensitivity enhancer Same as above 3. Spectral sensitizer, pages 23 to 24, page 648, right column to supersensitizer, page 649, right column 4. Whitening agent Page 24 5. Antifoggants and stabilizers pages 24 to 25, page 649, right column 6. Light absorbers, filter dyes 25 to 26 pages 649 right column to UV absorbers 650 page left column 7. Anti-staining agent Page 25 Right column Page 650 Left-right column 8. Dye image stabilizer page 25 9. Hardener 26 pages 651 left column 10. Binder page 26 Same as above 11. Plasticizer, lubricant Page 27 Page 650 Right column 12. Coating aid, surface active agent, pages 26 to 27, same as above 13. Antistatic Agent Page 27 As above As a support that can be used in the silver halide photographic light-sensitive material of the present invention, cellulose acetate, cellulose nitrate,
Examples thereof include polyester such as polyethylene terephthalate, polyolefin such as polyethylene, polystyrene, baryta paper, paper coated with polyolefin, glass and metal. These supports are subjected to a surface treatment if necessary.

As a method for imagewise exposing the silver halide photographic light-sensitive material according to the present invention, a plate-making camera equipped with a halogen lamp or a quinocene light source, a laser light source such as an Ar laser, a HeNe laser or a semiconductor laser, or an LED is used. There is a method of exposing with a plate making scanner, plotter, typesetting machine, etc., and a plate making printer installed.

The silver halide photographic light-sensitive material according to the present invention can be subjected to development processing by various methods such as a commonly used method after exposure.

The black-and-white developing solution is an alkaline solution containing a developing agent such as hydroxybenzenes, aminophenols and aminobenzenes, and sulfites, carbonates, bisulfites of other alkali metal salts, JP-A-56, -106244, amino compounds, bromides, iodides and the like can be included. The pH of the developer is preferably 9.5 to 12.0.

As the fixing liquid, those having a generally used composition can be used. The fixer is generally an aqueous solution containing a fixer, a hardener, and others, and the pH is usually 3.8 to 6.0. Examples of the fixing agent include thiosulfates such as sodium thiosulfate, potassium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate, potassium thiocyanate and ammonium thiocyanate, and organic sulfur compounds capable of forming a soluble stable silver complex salt. A known fixing agent can be used.

The fixing solution is a water-soluble aluminum salt which acts as a hardening agent, such as aluminum chloride, aluminum sulfate, potassium alum, aldevides or sulfite adducts thereof.

In the present invention, a fixing solution containing no hardener may be used. In that case, the pH is usually 4.2 ~
It is 7.0.

Further, the processing method of the present invention is applied when an automatic processor is used, and is preferable in the case of rapid processing where the processing time is short. For quick processing, Dry to Dry is 90 seconds or less,
It is preferably 20 seconds to 70 seconds.

[0072]

The present invention will be described in detail with reference to the following examples. As a matter of course, the present invention is not limited to the embodiments described below.

Example 1 (Preparation of Support Having Conductive Layer) Subbed Thickness
8 W / (m ² · min) for 100 μm polyethylene terephthalate
After the corona discharge with the energy of 1., the antistatic liquid having the following constitution was applied at a speed of 70 m / min using a roll-fit coating pan and an air knife so as to have the following coating amount.

Water-soluble conductive polymer P 0.6 g / m ² Hydrophobic polymer particles L 0.4 g / m ² Polyethylene oxide compound Ao 0.06 g / m ² Curing agent E 0.2 g / m ² This was dried at 90 ° C. for 2 minutes Heat treatment was performed at 140 ° C for 90 seconds. What prepared this conductive layer apply | coated to one side of the support body was prepared.

[0075]

[Chemical 17]

(Preparation of silver halide photographic emulsion A) A silver iodobromide emulsion (2 mol% of silver iodide per mol of silver) was prepared by the simultaneous mixing method. During this mixing, K ₂ IrCl ₆ was added at 8 × 10 ^-7 mol per mol of silver. The resulting emulsion has an average grain size
The emulsion consisted of cubic monodisperse grains of 0.20 μm (variation coefficient 9%). 200 mg of sensitizing dye D-1 per 1 mol of silver
After the addition, the product was washed with water and desalted by a conventional method. 40 ° C pA after desalting
g was 8.0. Subsequently, 10 mg of D-2 was added per mol of silver, and further a mixture of the compounds [A], [B] and [C] was added to obtain an emulsion A. After that, sulfur sensitization was performed.

[0077]

[Chemical 18]

Formulation (1) (Photosensitive silver halide emulsion layer composition) Gelatin Amount shown in Table 1 Silver halide emulsion A Silver amount 3.2 g / m ² Stabilizer: 4-methyl-6-hydroxy-1,3, 3a, 7-Tetrazaindene 30mg / m ² Antifoggant: 5-nitroindazole 10mg / m ² 1-Phenyl-5-mercaptotetrazole 5mg / m ² Surfactant: Sodium dodecylbenzenesulfonate 0.1g / m ²

[0079]

[Chemical 19]

Hydrazine derivative of the present invention b-6 15 mg / m ² Hydrazine derivative of the present invention c-7 10 mg / m ²

[0081]

[Chemical 20]

[0082]

[Chemical 21]

Gelatin Amount shown in Table-1 Surfactant: sodium dodecylbenzenesulfonate 0.1 g /
m ² : S-1 6 mg / m ² colloidal silica 100 mg / m ² Hardener: E 55 mg / m ² Formulation (4) [Backing protective layer composition] Gelatin Amount shown in Table-1 Matting agent: Average particle size 5.0 μm of monodisperse polymethyl methacrylate a cleat 50 mg / m ² surfactant: ^S-2 10mg / m 2 hardener: glyoxal 25 mg / m ^2: a conductive layer on a support having a H-1 35mg / m ² conductive layer On the opposite side, an emulsion layer having the formulation (1) and an emulsion protective layer having the formulation (2) were coated in that order. A backing layer having the formulation (3) and a backing protective layer having the formulation (4) were sequentially applied to the conductive layer side and dried.

Then, using the following developing solution and fixing solution, development processing was carried out under the following conditions using a plate making automatic processor LD281Q (manufactured by Dainippon Screen).

The film was processed without exposure.

<Processing Conditions> The processing conditions are as follows.

Developer Formulation 1 Sodium bisulfite 40 g N-methyl-P-amonophenol sulfate 350 mg Ethylenediaminetetraacetic acid disodium salt 1 g Sodium chloride 5 g Potassium bromide 1.2 g Trisodium phosphate 75 g 5-Methylbenztriazole 250 mg 2 -Mercaptobenzthiazole 23 mg Benztriazole 83 mg Hydroquinone 29 g Diisopropylaminoethanol 2.3 ml Amine compound Am-1 0.5 ml Potassium hydroxide Amount to bring the pH of the working solution to 11.6 At the time of use, water was added to make 1 liter.

[0088]

[Chemical formula 22]

Fixer formulation Ammonium thiosulfate (59.5% W / V aqueous solution) 830 ml Ethylenediaminetetraacetic acid disodium salt 515 mg Sodium sulfite 63 g Boric acid 22.5 g Acetic acid (90% W / V aqueous solution) 82 g Citric acid (50% W / V aqueous solution) ) 15.7g Gluconic acid (50% W / W aqueous solution) 8.55g Aluminum sulphate (48% W / W aqueous solution) 13ml Glutaraldehyde 3g Sulfuric acid The pH of the working solution is 4.6. ..

Development processing conditions Each process time includes the wading transport time until the next process.

The replenisher used had the same composition as that of the developer and fixer, and the sample was treated for 400 m ² while replenishing at a rate of 240 cc / m ^{2 for} fixing and 380 cc / m ² for fixing, and then the stain on the roller and the film The stain and the uneven development state were observed. The observations were ranked by visual judgment evaluation as follows.

A. Best B. Good C. Slightly inferior D. Inferior The result is as follows.

If at least one of the three evaluations is C or D, it is not a practically acceptable level.

[0094]

[Table 1]

From the results shown in Table 1, it can be seen that the samples of the present invention are evaluated in terms of roller, film stain, and development unevenness.

Example 2 (Preparation of Support Having Conductive Layer) Corona discharge was applied on a polyethylene terephthalate support having a thickness of 100 μ and subjected to an undercoating treatment, and then a conductive layer having the following constitution was applied.

Gelatin 35 mg / m ² SnO ₂ / Sb (8/2) (particle size 0.3 μm) 250 mg / m ²

[0098]

[Chemical formula 23]

This was dried at 90 ° C. for 2 minutes and heat-treated at 140 ° C. for 90 seconds. The conductive layer coated on only one side of the support was prepared.

(Preparation of silver halide photographic emulsion B) A silver chlorobromide emulsion (60 mol% of silver chloride per mol of silver) was prepared by the simultaneous mixing method. During this mixing, K ₂ IrCl ₆ was added at 8 × 10 ^-7 mol per mol of silver. The resulting emulsion has an average grain size
The emulsion consisted of cubic monodisperse grains of 0.20 μm (variation coefficient 9%). After rinsing with water and desalting by a conventional method, sulfur sensitization was performed.

(Preparation of silver halide photographic light-sensitive material) On the surface opposite to the side coated with the above-mentioned conductive layer, a silver halide emulsion layer of the following formula (5) was added with a gelatin amount of 1.7 g / m ² ,
It is coated so that the amount of silver is 3.2 g / m ^2, and the emulsion protective layer of the following formulation (6) is further coated thereon so that the amount of gelatin is 1.0 g / m ^2, and on the other side. On the other undercoat layer, a backing layer is coated according to the following prescription (7) so that the amount of gelatin is 2.0 g / m ^2, and a backing protective layer of the following prescription (8) is further applied on it. Was applied so as to be 1 g / m ² to obtain sample Nos. 1 to 18.

Formulation (5) (Silver halide emulsion layer composition) Gelatin 1.7 g / m ² Silver halide emulsion B Silver amount 3.2 g / m ²

[0103]

[Chemical formula 24]

Stabilizer: 4-methyl-6-hydroxy-1,3,3a, 7-tetrazaindene 30 mg / m ² Antifoggant: 5-nitroindazole 20 mg / m ² 1-phenyl-5-mercaptotetrazole 5 mg / M ² Surfactant: saponin 0.1g / m ²

[0105]

[Chemical 25]

30 mg of the hydrazine derivative C-8 according to the present invention
/ M ²

[0107]

[Chemical formula 26]

Formulation (6) (backing layer composition)

[0109]

[Chemical 27]

Gelatin 2.4 g / m ² Surfactant: Saponin 0.1 g / m ² : S-1 6 mg / m ² Colloidal silica 100 mg / m ² Formulation (7) [Backing protective layer composition] Gelatin 1 g / m ² matting agent average particle size: 5.0μm monodisperse polymethyl methacrylate a cleat 50 mg / m ^{2 surfactant: S-2 10mg / m 2} S-3 5mg / m 2 hardener: glyoxal ^{25mg / m 2: H-1} 35mg / m ^{2 The} obtained sample was brought into close contact with a step wedge, exposed with a HeNe laser for 10 ^-6 seconds, and then a developing solution and a fixing solution having the composition shown below were added to Konica Corporation's automatic development for rapid processing. Processing was performed on the GR-26SR machine under the following conditions.

Developer Formulation Ethylenediaminetetraacetic acid sodium salt 1g Sodium sulfite 60g Boric acid 40g Hydroquinone 35g Sodium hydroxide 8g Sodium bromide 3g 5-Methylbenzotriazole 0.2g 2-Mercaptobenzothiazole 0.1g 2-Mercaptobenzothiazole- 5-Sulfonic acid 0.2g 1-Phenyl-4,4-dimethyl-3-pyrazolidone 0.2g Add water and adjust the pH with 1l sodium hydroxide 10.6 Fixer formulation Ammonium thiosulfate (72.5% W / V aqueous solution) 240ml Sodium sulfite 17 g Sodium acetate / trihydrate 6.5 g Boric acid 6.0 g Sodium citrate / dihydrate 2.0 g When the fixing solution was used, the above composition A and composition B were dissolved in 500 ml of water in this order to make 1 liter. The pH of this fixer was adjusted to 6.0 with acetic acid.

(Development processing conditions) The same test as in Example 1 was performed using the obtained sample.

As a result, it was found that the sample of the present invention gave better results than the comparative sample.

[0114]

Industrial Applicability According to the present invention, it is possible to provide a processing method for super-high-contrast silver halide black-and-white photographic light-sensitive material that does not cause sludge and processing defects in processing by an automatic processor.

Claims (1)

[Claims] 1. A processing method in which a silver halide black and white photographic light-sensitive material having at least one silver halide emulsion layer on a support is imagewise exposed, processed with a developing solution, and then processed with a processing solution having a fixing ability. In the constitution layer of the silver halide black-and-white photographic light-sensitive material, the processing solution having a hydrazine derivative and / or the fixing ability contains a nonionic surfactant. Processing method of silver halide black and white photographic light-sensitive material.